Polymer

ABSTRACT

The present application relates to a polymer and a use thereof. The present application may provide a functional polymer which expresses a low solubility to a polar solvent and a non-polar solvent. If applied to the use of cosmetics such as mascara or to medical uses, the polymer in the present application may express a tolerance to diverse solvents such as sebum, sweat, tears and the like, and thus enables makeup to last, etc. Accordingly, the polymer may be applied to diverse uses and used in film forming agents, cosmetic compositions, or cosmetics, or the like.

CROSS-REFERENCE TO RELATED APPLICATIONS

The present application is a national phase entry under 35 U.S.C. § 371of International Application No. PCT/KR2015/013738, filed Dec. 15, 2015,which claims of priority from Korean Patent Application No. 2014-0180726filed on Dec. 15, 2014, the disclosures of which are herein incorporatedby reference.

TECHNICAL FIELD

The present application relates to a polymer and a film forming agentcomprising the polymer.

Background Art

There is a case that functional polymers are required in preparingcosmetics or drugs. For example, in cosmetics such as mascara, orcosmetics or drugs that are applied to other skins, polymers havingresistance to solvents of different properties such as sweat, tears andsebum may be required. Polymers, which are applied in preparingcosmetics, are described in Patent Documents 1 and 2.

PRIOR ART DOCUMENTS Patent Documents

Patent Document 1: Japanese Unexamined Patent Publication No.2000-119140

Patent Document 2: Japanese Unexamined Patent Publication No.2003-055136

DISCLOSURE Technical Problem

The present application provides a polymer and a film forming agentcomprising the polymer. It is one main object of the present applicationto provide a functional polymer which is applied to cosmetics, such asmascara, or articles to be used in human bodies, such as medicalsupplies, by exhibiting a low solubility in both polar solvents andnon-polar solvents to have resistance to sweat and sebum and the likeand a film forming ability suitable to the above applications, and a usethereof.

Technical Solution

The polymer of the present application exhibits a low solubility inpolar solvents and non-polar solvents. In the present application, theterm non-polar solvent means a solvent having a dielectric constant at25° C. in a range of about 1 to about 3, about 1.5 to 2.5 or about 1.5to 2 or so, and the term polar solvent means a solvent having adielectric constant at 25° C. in a range of about 75 to about 85 orabout 75 to 80. A representative example of the non-polar solvent ishexane (dielectric constant (25° C.): about 1.89), and a representativeexample of the polar solvent is water (dielectric constant (25° C.):about 78.54), without being limited thereto. In chemistry, thedielectric constant for the solvent is known for each solvent.

In one example the polymer may have solubility in the polar solvent of10 or less, or 5 or less. In one example the polymer may have solubilityin the non-polar solvent of 10 or less, or 5 or less. It means that thelower the value of the solubility, the polymer has more excellentresistance against the corresponding solvent, so that the lower limit isnot particularly limited. For example, the solubility in the polarsolvent and the non-polar solvent may be about 0.001 or more, about 0.01or more, about 0.1 or more, or about 1 or more, respectively. In thepresent application, solubility in a specific solvent refers to grams(g) of a polymer that can be dissolved in 100 g of the correspondingsolvent as much as possible. Furthermore, unless otherwise specified,the solubility in the present application refers to solubility measuredat room temperature. In the present application the term roomtemperature is a natural temperature without warming or cooling, and forexample, may be a temperature in a range of about 10° C. to 30° C.,about 15° C. to 30° C., or about 20° C. to 30° C., or a temperature ofabout 25° C. or so. In the case of the characteristic, the value ofwhich varies depending on temperatures, such as the solubility, amongcharacteristics mentioned in this specification, the correspondingcharacteristic is a characteristic at room temperature, unless otherwisespecified.

The polymer can exhibit solubility in the intermediate step solventsbetween the polar and non-polar solvents. For example, the polymer mayhave solubility in a range of 15 or more or about 15 to 50 in thesolvent having a dielectric constant at 25° C. in a range of 4 to 15, 5to 15, 5 to 10, 5 to 8 or about 5 to 6.5. Such a solvent may beexemplified by ethyl acetate (dielectric constant (25° C.): about 6.02)and the like, without being limited thereto.

The polymer may be, for example, through adjusting the types of monomersforming the polymer and the proportions thereof.

For example, the polymer may comprise polymerized units of a firstmonomer having a homopolymer solubility parameter of less than 10.0(cal/cm³)^(1/2) and polymerized units of a second monomer of less than10.0 (cal/cm³)^(1/2) or more.

In the present application the solubility parameter refers to asolubility parameter of a homopolymer prepared by polymerizing thecorresponding monomer, through which the degree of hydrophilicity andhydrophobicity in the corresponding monomer may be found out. A methodof obtaining the solubility parameter is not particularly limited, andmay be in accordance with a method known in the art. For example, theparameter may be calculated or obtained according to the method known inthe art as the so-called HSP (Hansen solubility parameter). Here, inanother example, the homopolymer solubility parameter of the firstmonomer may be in a range of 5 (cal/cm³)^(1/2) to 9.5 (cal/cm³)^(1/2) or7 (cal/cm³)^(1/2) to 9 (cal/cm³)^(1/2). Here, in another example, thehomopolymer solubility parameter of the second monomer may be in a rangeof 10 (cal/cm³)^(1/2) to 15 (cal/cm³)^(1/2) or 10 (cal/cm³)^(1/2) to 13(cal/cm³)^(1/2). By appropriately applying the monomers havingsolubility parameters of these ranges, it is possible to form thepolymer representing the above-described characteristics.

In addition, in the present application the polymerized unit of anymonomer or compound means a form in which the monomer or compound isincluded in the polymer as a monomer unit via a polymerization reaction.

The monomer usable as the first monomer by having the above solubilityparameter may be exemplified by alkyl (meth)acrylate or aromatic(meth)acrylate. In the present application the term (meth)acrylate maymean acrylate or methacrylate.

An alkyl group included in the alkyl (meth)acrylate may be exemplifiedby a straight, branched or cyclic alkyl group having 1 to 20 carbonatoms, 4 to 20 carbon atoms, 8 to 20 carbon atoms or 10 to 20 carbonatoms and the alkyl group may be optionally substituted by one moresubstituents. Such a monomer may be exemplified by methyl(meth)acrylate, ethyl (meth)acrylate, n-propyl (meth)acrylate, isopropyl(meth)acrylate, n-butyl (meth)acrylate, t-butyl (meth)acrylate,sec-butyl (meth)acrylate, pentyl (meth)acrylate, 2-ethylhexyl(meth)acrylate, 2-ethylbutyl (meth)acrylate, n-octyl (meth)acrylate,isobutyl isobornyl (meth)acrylate, isooctyl (meth)acrylate, isononyl(meth)acrylate or lauryl (meth)acrylate, or the like, without beinglimited thereto.

The aromatic (meth)acrylate may be exemplified by aryl (meth)acrylate orarylalkyl (meth)acrylate. Here, an aryl group of aryl or arylalkyl maybe, for example, an aryl group having 6 to 24 carbon atoms, 6 to 18carbon atoms or 6 to 12 carbon atoms. In addition, an alkyl group of thearylalkyl may be, for example, an alkyl group having 1 to 20 carbonatoms, 1 to 16 carbon atoms, 1 to 12 carbon atoms, 1 to 8 carbon atomsor 1 to 4 carbon atoms. Here, the alkyl group may be straight, branchedor cyclic, and the alkyl group or the aryl group may be optionallysubstituted by one or more substituents.

The aryl group or arylalkyl group can be exemplified by a phenyl group,a phenylethyl group, a phenylpropyl group or a naphthyl group, but isnot limited thereto.

The first monomer may be exemplified, for example, by a compoundrepresented by Formula 1 below.

In Formula 1 Q may be hydrogen or an alkyl group, and B may be astraight or branched alkyl group having 4 or more carbon atoms or aalicyclic hydrocarbon group, or an aromatic substituent such as the arylgroup or the arylalkyl group.

In Formula 1, the alkyl group present in Q may be exemplified by analkyl group having 1 to 20 carbon atoms, 1 to 16 carbon atoms, 1 to 12carbon atoms, 1 to 8 carbon atoms or 1 to 4 carbon atoms. The alkylgroup may be straight, branched or cyclic. The alkyl group may beoptionally substituted with one or more substituents.

In Formula 1, B may be a straight or branched alkyl group having 4 ormore carbon atoms, 6 or more carbon atoms or 8 or more carbon atoms.Such a compound comprising the relatively long-chain alkyl group isknown as a hydrophobic compound. The upper limit of the number of carbonatoms in the straight or branched alkyl group is not particularlylimited, and for example, the alkyl group may be an alkyl group havingup to 20 carbon atoms.

In another example, B in Formula 1 may be an alicyclic hydrocarbongroup, for example, an alicyclic hydrocarbon group having 3 to 20 carbonatoms, 3 to 16 carbon atoms or 6 to 12 carbon atoms, and an example ofsuch a hydrocarbon group may be exemplified by an alicyclic alkyl group,and the like, having 3 to 20 carbon atoms, 3 to 16 carbon atoms or 6 to12 carbon atoms such as a cyclohexyl group or an isobornyl group. Such acompound comprising the alicyclic hydrocarbon group is also known as arelatively hydrophobic compound.

In the present application, the substituent, which may be optionallysubstituted on an alkyl group, an alkylene group, an aromaticsubstituent in Formula 1 above, or Formula 2 or 3 to be described below,may be exemplified by halogen such as chlorine or fluorine, a glycidylgroup, an epoxy group such as an epoxyalkyl group, a glycidoxypropylgroup or an alicyclic epoxy group, an acryloyl group, a methacryloylgroup, an isocyanate group, a thiol group, an alkyl group, an alkenylgroup, an alkynyl group or an aryl group, and the like, but is notlimited thereto.

An appropriate type may be selected from the above monomers inconsideration of the physical properties of the desired polymer andused.

As the second monomer, it is possible to use a monomer selected frommonomers known to have the above described solubility parameter.

For example, as the second monomer, a compound represented by Formula 2or 3 below may be used.

In Formula 2, Q is hydrogen or an alkyl group, U is an alkylene group, Zis hydrogen or an alkyl group, and m is any number:

In Formula 3, Q is hydrogen or an alkyl group, A and U are eachindependently an alkylene group, X is a hydroxy group or a cyano groupand n is any number.

In Formulas 2 and 3, the alkylene group may be exemplified by analkylene group having 1 to 20 carbon atoms, 1 to 16 carbon atoms, 1 to12 carbon atoms, 1 to 8 carbon atoms or 1 to 4 carbon atoms. Thealkylene group may be straight, branched or cyclic. The alkylene groupmay be optionally substituted by one or more substituents.

In Formulas 2 and 3, the alkyl group present in Q and Z may beexemplified by an alkyl group having 1 to 20 carbon atoms, 1 to 16carbon atoms, 1 to 12 carbon atoms, 1 to 8 carbon atoms or 1 to 4 carbonatoms. The alkyl group may be straight, branched or cyclic. In addition,the alkyl group may be optionally substituted with one or moresubstituents.

In Formulas 2 and 3, m and n may be any number, and for example, eachindependently a number in a range of 1 to 100, 1 to 90, 1 to 80, 1 to70, 1 to 60, 1 to 50, 1 to 40, 1 to 30, 1 to 20, 1 to 16 or 1 to 12.

In one example, as the second monomer, a compound, wherein in Formula 2above Q is hydrogen or an alkyl group having 1 to 4 carbon atoms, U isan alkylene group having 1 to 4 carbon atoms, Z is hydrogen or an alkylgroup having 1 to 4 carbon atoms, and m is 1 to 30, may be used, but isnot limited thereto.

The polymer may be prepared by polymerizing the first and secondmonomers in an appropriate ratio. For example, the polymer may comprise50 to 99.9 parts by weight of the polymerized units of the first monomerand 0.1 to 20 parts by weight of the polymerized units of the secondmonomer. Here, in another example, the polymerized units of the firstmonomer may exist in 60 to 99.9 parts by weight, 70 to 99.9 parts byweight or 80 to 99.9 parts by weight. In addition, the polymerized unitsof the second monomer may be contained in 5 to 20 parts by weight or 7to 20 parts by weight. In the present application, the unit part byweight may mean a ratio of weight between the respective components,unless otherwise specified. Furthermore, the weight ratio of thepolymerized units of the monomer may mean the weight ratio of themonomer applied on preparing the polymer. Thus, for example, the phrasethe polymer comprises 50 to 99.9 parts by weight of polymerized units ofthe first monomer and 0.1 to 20 parts by weight of polymerized units ofthe second polymer may mean that the polymer has been formed bypolymerizing the monomer mixture comprising the first monomer and thesecond monomer in a weight ratio of 50˜99.9:0.1˜20 (first monomer:second monomer). If the weight ratio of the second monomer in thepolymer is less than 0.1 parts by weight or the weight ratio of thefirst monomer is more than 99.9 parts by weight, the resistance to theoil-based solvent or the sebum proofness may not be enough, and if theweight ratio of the second monomer exceeds 20 parts by weight or theweight ratio of the first monomer is less than 50 parts by weight, thepolymer cannot be formed by the phase separation, or the resistance tothe polar solvent or the resistance to sweat or tears may not be enough.

In another example, the polymer may comprise at least 50%, at least 55%,at least 60%, at least 65%, at least 70%, at least 75% or at least 80%,of polymerized units of the first monomer, based on weight. The ratio ofpolymerized units of the first monomer may be 99% or less, 98% or less,97% or less, 96% or less, 95% or less, 94% or less, 93% or less, 92% orless, 91% or less, or 90% or less, based on weight. In the above state,the polymer may comprise the polymerized units of the second monomer ina ratio of 40 parts by weight or less, 35 parts by weight or less, 30parts by weight or less, 25 parts by weight or less, 20 parts by weightor less, 15 parts by weight or less, 10 parts by weight or less or about8 parts by weight or less relative to 100 parts by weight of thepolymerized units of the first monomer. The polymerized units of thesecond monomer may be contained in a ratio of at least about 0.1 partsby weight, at least 0.15 parts by weight, at least 0.2 parts by weightor at least 5 parts by weight ratio relative to 100 parts by weight ofthe polymerized units of the first monomer. While the resistance to theoil-based solvent or the sebum proofness is secured in the above ratio,the resistance to the polar solvent, or the resistance to sweat or tearsor the like can be also effectively secured.

The polymer may comprise additional monomers for imparting otherfunctions, for example, controlling glass transition temperature, etc.in addition to the above-described first and second monomers.

The polymer can be produced by a known polymerization method using thefirst and second monomers. In one example the polymer may be prepared bya solution polymerization method using a solvent, for example, anorganic solvent, for example a radical solution polymerization method.For example, when the polymer is applied to an application in contactwith a human body such as cosmetics, as a solvent in the polymerizationprocess, a solvent friendly to the human body can be selected and used.Such a solvent may be exemplified by isododecane, isoparaffin orisohexadecane, and the like, but is not limited thereto.

In the present application the polymer may have a weight averagemolecular weight (Mw) in a range of 10,000 to 500,000. In the presentapplication, the weight average molecular weight may be, for example, aconverted value of the standard polystyrene measured using GPC (GelPermeation Chromatograph), and the term molecular weight can refer tothe weight average molecular weight, unless otherwise specified. Forexample, when the polymer is applied as a film forming agent, the abovemolecular weight (Mw) may be useful. By using the polymer in the abovemolecular weight (Mw) range, it is possible to form a film efficientlywithout an agglomeration phenomenon and the like.

In the present application the polymer may have a glass transitiontemperature of 10° C. or more. In another example, the glass transitiontemperature may be 15° C. or more, 20° C. or more, 25° C. or more, or30° C. or more. The glass transition temperature of the polymer may beabout 110° C. or less, about 100° C. or less, 90° C. or less, 80° C. orless, 70° C., 60° C. or less, or 55° C. or less. In the presentapplication, the glass transition temperature is a theoretical valueobtained through the so-called Fox equation from the monomer compositionof the polymer. For example, when the polymer is applied as a filmforming agent, the above glass transition temperature may be useful. Byusing the polymer in the above glass transition temperature range, it ispossible to form a film efficiently without a stickiness or brittlenessphenomenon and the like.

The present application also relates to a film forming agent, a cosmeticcomposition or a cosmetic, comprising the polymer. If theabove-described polymer is used, it is possible to form a uniform film(coating) by application, to exhibit high stability even when applied toskin, and to show excellent resistance to various solvents such assweat, tears or sebum by exhibiting a resistance to both polar andnon-polar solvents.

Accordingly, the polymer can be applied to prepare a film forming agentor a cosmetic composition capable of being used in producing variouscosmetics, including, cosmetic packs, make-ups, such as mascara, appliedto lips or eyes, nail polishes which can be applied to fingernails ortoenails, lipsticks, eye shadows, hair styling products or eyeliners,etc. In addition, the polymer or the film forming agent or the like mayalso be applied to a medicinal use, and the medicinal use may beexemplified by bandages or transdermal absorption formulations and thelike.

The ratio of the polymer in the film forming agent, the cosmeticcomposition or the cosmetic is not particularly limited, which may beselected in consideration of application purpose. For example, if thepolymer is applied to the cosmetic composition, the concentration of thepolymer in the composition may be in the range of 1% by weight to 20% byweight, but is not limited thereto.

The film forming agent, the cosmetic composition or the cosmetic mayfurther comprise other active ingredients depending on applications.Additional active ingredients may also be exemplified by medicinalingredients, physiologically active ingredients or pharmacologicallyactive ingredients as well as cosmetic ingredients such as whitening orsunscreen. Such an active ingredient may be exemplified by topicalanesthetic ingredients (lidocaine, dibucaine hydrochloride, dibucaine,ethyl aminobenzoate, etc.), analgesic ingredients (salicylic acidderivatives such as methyl salicylate, indomethacin, piroxicam,ketoprofen, felbinac, etc.), anti-inflammatory ingredients(glycyrrhizinic acid, salts glycyrrhizinate such as dipotassiumglycyrrhizinate, glycyrrhetinic acid, stearyl glycyrrhetinate,bufexamac, benzyl nicotinate, hydrocortisone, hydrocortisone butyrate,hydrocortisone acetate, prednisone valeroacetate, prednisone acetate,prednisone, dexamethasone, dexamethasone acetate, dimethyl isopropylazulene ibuprofenpiconol, amika extract, Scutellaria Baicalensis Rootextract, cattail ear extract, chamomile extract, calamine, licoriceextract, guaiazulene, gardenia extract, gentiana extract, black teaextract, tocopherol, tocopheryl acetate, lithospermum extract, perillaextract, peony extract, sage extract, Swertia japonica extract, MulberryRoot extract, pyridoxine hydrochloride, peach leaf extract, cornflowerextract, saxifrage extract, mugwort extract, roman chamomile extract,etc.), anti-histamine ingredients (chlorpheniramine maleate,diphenhydramine, diphenhydramine hydrochloride, diphenhydraminesalicylate, ISO pen zyl hydrochloride, etc.), local irritationingredients (ammonia, 1-menthol, dl-can full, peppermint oil, nicotinicacid, benzyl niconinate, nonylic acid vanilylamide, etc.), antipruriticingredients (crotamiton etc.), preservative or sterilizing ingredients(acrinol, chlorhexidine gluconate, chlorhexidine hydrochloride,benzalkonium chloride, benzethonium chloride, povidone iodine, iodoform,iodine, potassium iodide, merbromin, oxides, cresol, triclosan, phenol,isopropyl methyl phenol, thymol, sodium salicylate, undecylenic acid,photosensitizer, hinokitiol, phenoxyethanol, chlorobutanol, quaternium73, zinc pyrithione, para-hydroxybenzoic acid esters, eucalyptusextract, resorcin rosemary extract, etc.), antifungal ingredients(imidazole-based antifungal agenst, such as clotrimazole, clotrimazoleacetate, miconazole acetate, econazole acetate, befornazole, oxiconazoleacetate, sulconazole acetate, neticonazole hydrochloride, befornazoleand tioconazole, omoconazole acetate, allylamine-based antifungalagents, such as terbinafine, terbinafine hydrochloride and naftifine,benzylamine-based antifungal agents such as butenafine, allylamine-basedantifungal agents such as amorphin hydrochloride, thiocarbamicacid-based antifungal agents such as tolnaftate, tolciclate,pyrrolnitrine, exalamide, cyclopirox olamine, etc.), tissue-repairingingredients (allantoin, heparin-like substances, vitamin A palmitate,vitamin D2, retinol acetate, retinol, vitamin A oil, panthenol, etc.),astringent ingredients (zinc oxide, Acanthopanax senticosus extract,aluminum chloride, yellow gourd extract, salts thereof, citric acid,white birch extract, tea extract, hop extract, horse chestnut extract,etc.), dead skin flexibilizer ingredients (urea, glycerin, concentratedglycerin, potassium hydroxide, salicylic acid, sulfur, colloidal sulfur,resorcin, glycolic acid, lactic acid, sodium sulfate, etc.),moisturizing ingredients (butylene glycol, pyrrolidone sodiumcarboxylate, propylene glycol, ribonucleic acid sodium, Angelica utilisextract, asparaginic acid, alanine, arginine, sodium alginate, althaeaextract, aloe vera extract, oyster-extract, hydrolyzed keratin,hydrolyzed collagen, hydrolyzed conchiolin, hydrolyzed egg shellmembrane, hydrolyzed albumen, hydrolyzed silk, brown algae extract,quince extract, bramble extract, xylitol, chitosan, cucumber extract,quince seed extract, glycine, glycerin, glucose, cape aloe extract,cystin, cysteine, mallow extract, serine, sorbitol, trehalose, sodiumlactate, sodium hyaluronate, placenta extract, sponge gourd extract,multi fee, mannitol, lily extract, lactoferrin, lysine, apple extract,royal jelly extract, etc.), emollient ingredients (almond oil, avocadooil, olive oil, oleic acid, orange roughy oil, cacao butter, carrotextract, squalane, ceramide, evening primrose oil, grape seed oil,jojoba oil, macadamia nut oil, mineral oil, mink oil, eucalyptus oil,rosehip oil, vaseline, etc.), whitening ingredients (ascorbic acid,ascorbic acid derivatives, arbutin, recinol, ellagic acid, glutathione,kojic acid, rose fruit extract, kiwi extract, etc.), ultravioletprotective ingredients (para-aminobenzoic acid, para-aminobenzoic acidethyl ester, para-aminobenzoic acid glycerin ester,para-dimethylaminobenzoic acid amyl alcohol ester,para-dimethylaminobenzoic acid 2-ethylhexyl alcohol ester,t-butylmethoxydibenzoyl methane, oxybenzones, octyl triazone, octylsalicylate, ethyl diisopropyl cinnamate, methyl diisopropyl cinnamate,cinoxate, dimethoxy cinnamic acid glyceryl octanate, octyl dimethoxybenzylidene dioxoimidazolidine propionate, Chinese tea extract,drometrizole, isopropyl para-methoxycinnamate, homosalate, octyl methoxycinnamate, etc.), herbal extract ingredients, vitamins, amino acids orminerals, without being limited thereto.

The film forming agent, the cosmetic composition or the cosmetic mayinclude other solvents, thinners or additives depending on applications.

Here, the solvent or thinner component may be exemplified depending onapplications of the composition, use forms, and the like, for example,by alcohols (e.g., polyethylene glycol, etc.), ethers (diethyl ether,etc.), glycol ethers (cellosolve species such as methyl cellosolve;dialkyleneglycol alkyl ethers such as diethylene glycol ethyl ether,etc.), nitriles (acetonitrile, etc.), ketones (acetone, etc.) or esters(carboxylic acid alkyl esters such as ethyl acetate, etc.).

In addition, the additive may be exemplified by not only plasticizer,wetting agents, antifoaming agents, coloring agents, preservatives,aromatics, flavors, pigments or thickeners but also common componentsused in quasi-drugs, pharmaceuticals or cosmetics, for example, powderybase materials or carriers (binders, disintegrants, excipients orlubricants and the like), oily base materials or carriers (animal andvegetable oils, waxes, vaseline, paraffin oils, silicone oils, higherfatty acid esters or higher fatty acids, etc.), aqueous base materialsor carriers (gel base materials, such as xanthan gum, etc.),preservatives, chelating agents, antioxidants, refreshing agents,stabilizers, fluidizers, emulsifiers, thickeners, buffering agents,dispersing agent, absorbents, moisturizing agents, wetting agents,desiccants, antistatic agents or other resins (polyamide-based resins,olefin-based resins such as hydrogenated polybutene, etc.), withoutbeing limited thereto.

The method for preparing the film forming agent, the cosmeticcomposition or the cosmetic using the above components or other knownadditional components, if necessary is not particularly limited, and aknown manner may be applied.

Advantageous Effects

The present application can provide a functional polymer showing a lowsolubility in polar and non-polar solvents. The polymer of the presentapplication may be applied to various uses, and for example, when it isapplied to cosmetics such as mascara, or other medicinal uses, it mayrepresent a resistance to various solvents, such as sebum, sweat andtears, so that it may be used in a film forming agent, a cosmeticcomposition or a cosmetic capable of maintaining durability such asmakeup.

MODE FOR INVENTION

Hereinafter, the polymers of the present application and the like willbe specifically explained through Examples and Comparative Examples, butthe scope of the polymer is not limited to the following examples. InExamples and Comparative Examples below, each physical property wasevaluated by the following methods.

1. Solubility Measurement of Polymer

Polymer solutions prepared in Examples or Comparative Examples are keptat a temperature of about 150° C. for about 60 minutes to volatilize thesolvent. 1 g of the polymer volatilizing the solvent is collected. 1 gof the above collected polymer is added to 5 g of a solvent (hexane,ethyl acetate, acetone or water) and stirred at room temperature for 30minutes, and then the remaining polymer, which is un-dissolved, isremoved. The transparent solution with removing the remaining polymer issampled and dried at 150° C. for 30 minutes to remove the solvent.Through mass comparison of the remaining polymer in the solutionremoving the solvent the solid content is calculated. The concentrationof the polymer dissolved in the solvent is measured through the solidcontent and the solubility is obtained by converting the measured amountto a value for 100 g of the solvent. If the solution is not transparenteven after removing the remaining polymer, the solution is passedthrough a filter (0.45 μm NYLON) to obtain the transparent solution, andthen the above process is carried out.

<Solubility Evaluation Criteria>

A: when the solubility is 15 or more

B: when the solubility is more than 10 and less than 15

C: when the solubility is more than 5 and up to 10

D: when the solubility is up to 5

2. Molecular Weight Measurement

The weight average molecular weight (Mw) and molecular weightdistribution (PDI) were measured under the following conditions by usingGPC, and the measurement results were converted by using the standardpolystyrene of Agilent system in preparing a calibration curve.

<Measurement Conditions>

Measuring instrument: Agilent GPC (Agilent 1200 series, U.S.)

Column: PL Mixed B two connected

Column temperature: 40° C.

Eluant: THF (Tetrahydrofuran)

Flow rate: 1.0 mL/min

Concentration: ˜1 mg/mL (100 μL injection)

3. Calculation of glass transition temperature

The glass transition temperature (Tg) was calculated depending on themonomer composition by the following Equation.1/Tg=ΣWn/Tn  <Equation>

wherein Wn is a weight fraction of each monomer in the polymer, Tn is aglass transition temperature appearing when the monomer has formed ahomopolymer, and the right-hand side of the equation is a result ofsumming all the calculated values after calculating the value (Wn/Tn)obtained by dividing the weight fraction of the used monomer by theglass transition temperature appearing when the monomer has formed ahomopolymer for each monomer.

4. Sebum Blurring Test

Composition A is prepared by dissolving a polymer prepared in eachpreparation example in isododecane as a solvent in a concentration ofabout 10% by weight, and dissolving ceresine, a synthetic wax and amicrocrystalline wax in concentrations of 7% by weight, 6% by weight and8% by weight, respectively at a temperature of about 90° C.Subsequently, Composition B is prepared by adding propylene carbonateand disteardimonium hectorite to the Composition A in concentrations of8% by weight and 2% by weight, respectively and dispersing themuniformly for 20 minutes. Subsequently, iron oxide (CI 77499) is addedthereto in a concentration of 6% by weight and then an appropriateamount of preservatives is added, followed by being dispersed for 30minutes and then slowly cooled to about 28° C., to prepare a mascaraformulation.

Sebum blurring test using the prepared mascara formulation was dividedinto an in-vitro test and an in-vivo test and carried out, the detailsof which are as follows.

In-Vitro Test

The mascara formulation is applied on a slide glass (glass plate) to athickness of 30 μm and then completely dried at room temperature. Afterdrying, water and sebum are dropped on the mascara by 0.1 g,respectively, and after being left to stand for 20 minutes, a cotton padis placed thereon and reciprocated 30 times with a force of 200 gf, andthen the degrees of being smeared on the cotton pad are compared andevaluated in accordance with the following criteria.

<Evaluation Criteria>

When the degrees of being smeared on the cotton pad were compared on ascale within a range of 0 to 5, by setting the case of smearing nomascara at all on the cotton pad to 5 and setting the case of applyingthe polymer of the following comparative example 1 as a control group(reference) to 3, the superior level relative to the control group wasquantified to one decimal place as a relative comparison betweensamples.

In-Vivo Test:

Images are taken 6 hours after applying the prepared mascara formulationon eyelashes of a test subject, compared and evaluated according to thefollowing criteria.

<Evaluation Criteria>

After a lapse of 6 hours, images are taken and shown as values byimage-analyzing blurring areas. On image-analyzing, the area of blurringwas quantified as a pixel unit and shown.

5. Water Resistance Test

The above prepared mascara formulation is applied on a slide glass(glass plate) to a thickness of 30 μm and then completely dried at roomtemperature, and the dried sample is immersed in water at roomtemperature for about 30 minutes and then taken out to evaluate thewater resistance depending on the following criteria according to massdecrease rates (=100×(1−B/A), unit:%, wherein A is the total mass of theslide glass applying the mascara formulation and B is the total mass ofthe slide glass measured after immersing it in water, then taking outand removing moisture).

<Evaluation Criteria>

A: when the mass decrease rate is at least 5%

B: when the mass decrease rate exceeds 5%

6. NMR Evaluation Method

0.1 g of the polymer solution prepared in Examples or ComparativeExamples is collected and dissolved in 1 mL of the following solvent forNMR, and ¹H-NMR is measured according to the manufacturer's manual byusing the following analysis instrument, whereby the components andconversion rate of the polymer can be identified. For example, when thenon-polymerized monomer is present, a —H peak derived from ═CH2 of adouble bond terminus in 1H-NMR spectrum is identified near at about 5.7ppm to 6.4 ppm, and it is possible to identify the components of theprepared polymer through the area of —H peaks derived from each polymerstructure.

<Measurement Conditions>

Analysis instrument: 500 MHz NMR (Varian Unity Inova 500), 1H-NMR

Concentration: 10˜20 mg/mL, solvent: CDCl3-d3

Temperature: 25° C.

Example 1

As shown in Table 1 below, a monomer mixture in which EHMA (ethylhexylmethacrylate), IBOMA (isobornyl methacrylate) and EOEOEA(ethoxyethoxyethyl acrylate) were mixed in a weight ratio(EHMA:IBOMA:EOEOEA) of 25:60:15 was introduced into isododecane as asolvent to have the total monomer concentration of 35% by weight, andsubsequently, the dissolved oxygen was removed by bubbling with nitrogenat room temperature for about 30 minutes together with stirring and thenitrogen bubbling was further carried out for about 40 minutes whileelevating the reaction mixture removing oxygen to a temperature of about70° C. If the temperature increased to 70° C. through the above process,the polymerization reaction proceeded while further introducing anappropriate amount of a thermal initiator (V-65) into isododecane as asolvent. After performing the reaction for about 24 hours, the reactionwas completed by decreasing the temperature to room temperature toobtain a polymer solution.

Examples 2 to 4 and Comparative Examples 1 to 3

The polymer solutions were obtained in the same manner as Example 1except that the monomer types and proportions of the monomer mixturewere changed as Table 1 below.

TABLE 1 Comparative Example Example 1 2 3 4 1 2 3 Polymer A B C D E F GEHA 15 LMA 20 15 12 EHMA 30 CHMA 75 IBOMA 60 74 75 66 EOEOEA 10 10 10 10PEGMA 6 12 TMSS 100 PVP 100 Mw 34 30 20 20 — — — Tg 39 31 38 42 40 175 —Content unit: g EHA: ethyl hexyl acrylate (homopolymer solubilityparameter: 8.4 (cal/cm³)^(1/2)) LMA: lauryl methacrylate (homopolymersolubility parameter: 8.2 (cal/cm³)^(1/2)) EHMA: ethylhexyl methacrylate(homopolymer solubility parameter: 8.3 (cal/cm³)^(1/2)) CHMA: cyclohexylmethacrylate (homopolymer solubility parameter: 7.9 (cal/cm³)^(1/2))IBOMA: isobornyl methacrylate (homopolymer solubility parameter: 8.1(cal/cm³)^(1/2)) EOEOEA: ethoxyethoxy ethylacrylate (homopolymersolubility parameter: 10.6 (cal/cm³)^(1/2)) PEGMA: polyethyleneglycolmonoethyl ether methacrylate (ethylene oxide unit addition mole: 9moles, homopolymer solubility parameter: 10.8 (cal/cm³)^(1/2)) TMSS:trimethylsiloxysilicate (homopolymer solubility parameter: 7.5(cal/cm³)^(1/2)) (Trimethyl siloxysilicate: Dow Corning MQ-1600 Resin)PVP: polyvinyl pyrrolidone (homopolymer solubility parameter: 11(cal/cm³)^(1/2), Aldrich K30) Mw: weight average molecular weight(×10000) Tg: glass transition temperature (unit: ° C.)

1. Evaluation of NMR

As a result of evaluating NMR for the polymer of Example 1 1H peaksderived from ═CH2 of the double bond terminus were little identified,whereby it can be confirmed that the polymerization has been carried outeffectively. In addition, —CH— peaks adjacent to —COO— of EHMA and IBOMAforming the polymer and peaks derived from —OCH2CH2O— of EOEOEA wereobserved in the region of 5.0 μm to 3.5 ppm, where an area value ofpeaks is 9. Furthermore, peaks derived from —CH2- of the side chain and—CH3 derived from the meta-position were identified in the region of 2.5ppm to 1.3 ppm as peaks having an area value of 36, and 1H peaksidentified from —CH2CH— and —CH2CH2- derived from the polymer backbone,were identified in the region of 1.3 ppm to 0.5 ppm as an area of 55.

For the polymer of Example 2, NMR was also equally evaluated. As aresult of evaluation, 1H peaks derived from ═CH2 of the double bondterminus were little identified, whereby it could be confirmed that thepolymerization has been carried out efficiently. In addition, —CH— peaksadjacent to —COO— of EHA and CHMA forming the polymer and peaks derivedfrom —OCH2CH2O— of EOEOEA were identified in the region of 4.8 ppm to3.4 ppm as an area value of 10. Furthermore, from —CH2- adjacent to—COO— of EHA forming the polymer, peaks having an area value of about 3were identified in the region o 2.5 ppm to 2.0 ppm, and from —CH2- ofthe side chain and —CH3 derived from the meta-position, peaks having anarea value of 57 were identified in the region of 2.0 ppm to 1.5 ppm.Furthermore, 1H area value identified from —CH2CH— and —CH2CH2- derivedfrom the polymer backbone was about 29 in 1.5 ppm to 0.5 ppm.

In the case of the polymer of Example 3, 1H peaks derived from ═CH2 ofthe double bond terminus were little identified. In addition, —CH2- and—CH— peaks adjacent to —COO— of LMA and IBOMA forming the polymer andpeaks derived from —OCH2CH2-O and —OCH3 of PEGMA appeared in the regionof 4.7 ppm to 3.3 ppm, and the area value of the peaks was 17.Furthermore, peaks from —CH2- of the side chain and —CH3 derived fromthe meta-position were identified in the region of 2.0 ppm to 1.5 ppm asan area value of 72, and the area value of 1H peaks identified from—CH2CH— derived from the polymer backbone was 11 in the region of 1.5ppm to 0.5 ppm.

In results of measuring NMR for the polymer of Example 4, 1H peaksderived from ═CH2 of the double bond terminus were also little observed.In addition, —CH2- and —CH— peaks adjacent to —COO— of LMA and IBOMAforming the polymer and peaks derived from —OCH2CH2O— of EOEOEA appearedin the region of 4.7 ppm to 3.3 ppm, and the area value of the peaks was9. Furthermore, from —CH2- of the side chain and —CH3 derived from themeta-position, peaks having an area value of 36 were identified in theregion of 2.0 ppm to 1.5 ppm, and 1H area value identified from —CH2CH—and —CH2CH2- derived from the polymer backbone was 55 in 1.5 ppm to 0.5ppm.

Meanwhile, in the case of Comparative Example 3, the polymerizationbetween monomers was not appropriately achieved, and monomers and thelike were precipitated in the polymerization process, and thus thesynthesis of the polymer was impossible.

2. Physical Property Evaluation Results

The results of measuring physical properties for each polymer ofExamples and Comparative Examples were summarized and described in Table2 below.

TABLE 2 Comparative Example Example 1 2 3 4 1 2 Polymer A B C D E FSolubility Hexane D C D D A D Ethyl acetate A A A A A D Acetone C D D DA D Water D D D D D A Sebum In-vitro 3.9 4.0 3.8 4.0 3.0 3.3 blurringIn-vivo 3200 3100 3200 3000 4500 3800 Water resistance test A A A A A B

It can be confirmed from the above results that in the case of thepolymer satisfying the requirements of the present application, itexhibits a low solubility in polar solvents (water, acetone) andnon-polar solvents (hexane) and exhibits an excellent solubility insolvents (ethyl acetate) having middle characteristics. Also, if such apolymer was applied, it was confirmed to have an excellent sebumresistance even in the sebum blurring test while securing waterresistance.

The invention claimed is:
 1. A polymer comprising polymerized units of afirst monomer having a homopolymer solubility parameter of in a range of5 (cal/cm³)^(1/2) to 9.5 (cal/cm³)^(1/2) and polymerized units of asecond monomer having a homopolymer solubility parameter of 10.0(cal/cm³)^(1/2) or more, wherein the second monomer is a compoundrepresented by Formula 2 or 3 below:

wherein Q is hydrogen or an alkyl group, U is an alkylene group, Z ishydrogen or an alkyl group, and m is a number in a range of 1 to 100,

wherein Q is hydrogen or an alkyl group, A and U are each independentlyan alkylene group, X is a hydroxy group or a cyano group, and n is anumber in a range of 1 to 100, wherein the polymer comprises at least 75parts by weight of the polymerized units of the first monomer, andwherein the solubility of the polymer at room temperature is 10 or lessin a solvent having a dielectric constant (25° C.) in a range of 1 to 3,and the solubility of the polymer at room temperature is 10 or less in asolvent having a dielectric constant (25° C.) in a range of 75 to
 85. 2.The polymer according to claim 1, wherein the solubility at roomtemperature is 5 or less in a solvent having a dielectric constant (25°C.) in a range of 1 to
 3. 3. The polymer according to claim 1, whereinthe solubility at room temperature is 5 or less in a solvent having adielectric constant (25° C.) in a range of 75 to
 85. 4. The polymeraccording to claim 1, wherein the solubility at room temperature is 15or more in a solvent having a dielectric constant (25° C.) in a range of4 to
 15. 5. The polymer according to claim 1, wherein the first monomerhas a homopolymer solubility parameter in a range of 7 (cal/cm³)^(1/2)to 9 (cal/cm³)^(1/2).
 6. The polymer according to claim 1, wherein thefirst monomer is alkyl (meth)acrylate or aromatic (meth)acrylate.
 7. Thepolymer according to claim 1, wherein the first monomer is a compoundrepresented by Formula 1 below:

wherein, Q is hydrogen or an alkyl group, B is a straight or branchedalkyl group having 4 or more carbon atoms, an alicyclic hydrocarbongroup, or an aromatic substituent.
 8. The polymer according to claim 7,wherein the aromatic substituent is an aryl group or an arylalkyl group.9. The polymer according to claim 7, wherein in Formula 1 Q is hydrogenor a methyl group and B is an alkyl group having 7 or more carbon atomsor an alicyclic hydrocarbon group having 6 to 18 carbon atoms.
 10. Thepolymer according to claim 1, wherein the second monomer has ahomopolymer solubility parameter in a range of 10.0 (cal/cm³)^(1/2) to15.0 (cal/cm³)^(1/2).
 11. The polymer according to claim 1, wherein thesecond monomer has a homopolymer solubility parameter in a range of 10.0(cal/cm³)^(1/2) to 13.0 (cal/cm³)^(1/2).
 12. The polymer according toclaim 1, wherein in Formula 2 Q is hydrogen or an alkyl group having 1to 4 carbon atoms, U is an alkylene group having 1 to 4 carbon atoms, Zis hydrogen or an alkyl group having 1 to 4 carbon atoms and m is anumber in a range of 1 to
 30. 13. The polymer according to claim 1,wherein the polymer comprises 0.1 to 20 parts by weight of thepolymerized units of the second monomer.
 14. The polymer according toclaim 1, wherein the polymer comprises 75 to 99.9 parts by weight of thepolymerized units of the first monomer and 5 to 20 parts by weight ofthe polymerized units of the second monomer.
 15. A film forming agentcomprising the polymer of claim 1.